CN102753653A

CN102753653A - Liquid crystalline medium

Info

Publication number: CN102753653A
Application number: CN2011800087762A
Authority: CN
Inventors: M·克拉森-麦米尔; M·布雷米尔; K·施奈德
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2010-02-09
Filing date: 2011-01-31
Publication date: 2012-10-24
Anticipated expiration: 2031-01-31
Also published as: JP2013518977A; GB2491063B; KR101821432B1; US20120305843A1; EP2534223A1; TWI534130B; EP2534223B8; JP5755661B2; KR20120130200A; CN102753653B; EP2534223B1; GB2491063A; DE102011009691A1; GB201215039D0; WO2011098224A1; TW201136885A; US9777216B2

Abstract

The invention relates to a liquid crystalline medium containing at least one compound of formula I, where R1, R1*, L1 and L2 have the meanings given in claim 1, and to the use of said medium for an active matrix display, in particular based on the VA, PSA, PS-VA, PALC, FFS or IPS effect.

Description

Liquid crystal media

The present invention relates to comprise the liquid crystal media of the compound of at least a formula I,

Wherein

R ¹And R ^1*Represent to have the alkyl or the alkoxyl group of 1-15 C atom separately independently of one another, wherein one or more CH in these groups ₂Group can also be separately independently of one another by-C ≡ C-,-CF ₂O-,-CH=CH-,

-O-,-CO-O-,-O-CO-so that the O atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms can also replace by halogen,

L ¹And L ²Represent F, Cl, CF separately independently of one another ₃Or CHF ₂

This type medium can be used in particular for having based on the electro-optical display of the active array addressing of ECB effect be used for IPS (face intra) indicating meter or FFS (fringing field switching) indicating meter.

Electrically conerolled birefringence, ECB effect (electrically controlled birefringence) or also have the principle of DAP (arrangement phase distortion) effect be described in 1971 first (M.F.Schieckel and K.Fahrenschon; " Deformation of nematic liquid crystals with vertical orientation in electrical fields "; Appl.Phys.Lett.19 (1971), 3912).The works that then also has J.F.Kahn (Appl.Phys.Lett.20 (1972), 1193) and G.Labrunie and J.Robert (J.Appl.Phys.44 (1973), 4869).

J.Robert and F.Clerc (SID 80 Digest Techn.Papers (1980); 30), J.Duchene (Displays 7 (1986), 3) and H.Schad (SID 82 Digest Techn.Papers (1982); 244) works shows that the elastic constant that mesomorphic phase must have high numerical value compares K ₃/ K ₁, the optical anisotropy Δ n of high numerical value and the dielectric anisotropy value of Δ ε≤-0.5, can be used in high information display element based on the ECB effect.The edge orientation (VA technology=vertical orientation) that has vertical plane based on the electrooptics display element of ECB effect.Dielectric negative liquid crystal media can also be used for utilizing the indicating meter of so-called IPS or FFS effect.

Utilize the indicating meter of ECB effect, as so-called VAN (vertically aligned nematic mode) indicating meter, for example structural shape MVA (multi-zone vertical alignment nematic, for example: Yoshide; H. etc., report 3.1: " MVA LCD for Notebook or Mobile PCs... ", SID 2004 International Symposium, Digest of Technical Papers; XXXV, I collects, 6-9 page or leaf, and Liu; C.T. etc., report 15.1: " A 46-inch TFT-LCD HDTV Technology... ", SID 2004 International Symposium, Digest of Technical Papers; XXXV, II collects, the 750-753 page or leaf), PVA (pattern vertical orientation; For example: Kim, Sang Soo, report 15.4: " Super PVA Sets New State-of-the-Art for LCD-TV ", SID2004 International Symposium; Digest of Technical Papers, XXXV, II collects, the 760-763 page or leaf); ASV (senior ultraphotic angle, for example: Shigeta, Mitzuhiro and Fukuoka, Hirofumi; Report 15.2: " Development of High Quality LCDTV ", SID 2004 International Symposium, Digest of Technical Papers, XXXV; II collects, the 754-757 page or leaf) indicating meter in, itself be confirmed as except IPS (face intra) indicating meter (for example: Yeo, S.D.; Paper 15.3: " ALC Dis-play for the TV Application ", SID 2004 International Symposium, Digest of Technical Papers, XXXV; II collects, the 758th and 759 page) and permanent known TN (twisted nematic) indicating meter outside, one of liquid-crystal display of current most important three kinds of novel types is particularly for TV applications.For example at Souk, Jun, SID Seminar2004; Seminar M-6: " Recent Advances in LCD Technology ", Seminar Lecture Notes, M-6/1 to M-6/26; And Miller, Ian, SID Seminar 2004; Seminar M-7: " LCD-Television ", Seminar Lecture Notes compares these technology among the M-7/1 to M-7/32 with common form.Although the time of response of modern ECB indicating meter has driven remarkable improvement of addressing method acquisition of (overdrive) through hypervelocity, for example: Kim, Hyeon Kyeong etc.; Report 9.1: " A 57-in.Wide UXGA TFT-LCD for HDTV Application ", SID 2004 International Symposium, Digest of Technical Papers; XXXV; I collects, the 106-109 page or leaf, but acquisition is fit to the time of response of video; Particularly in the switching of GTG, remain a problem that does not solve satisfactorily.

For for the industrial application of this effect in the electrooptical display cells, require mesomorphic phase must satisfy many requirements.It is especially important to moisture air and physical influence such as heat, infrared, visible light and the radiation of ultraviolet region and the chemical tolerance of direct current and alternating electric field here.

In addition, the available mesomorphic phase requires in the suitable temp scope, to have liquid crystal mesomorphous phase and LV in the industry.

There is not the single compound that meets all these requirements in disclosed so far a series of compound with liquid crystal mesomorphous phase.Therefore, prepare two kinds to 25 kinds, preferred three kinds of mixtures usually, to obtain to be used as the material of mesomorphic phase to 18 kinds of compounds.Yet, because it is capable of using not have the liquid crystal material of remarkable negative dielectric anisotropic and enough permanent stability up to now, so can not easily prepare best phase by this way.

Array liquid crystal display (MFK indicating meter) is known.As the non-linear element that is used for single pixel independent translation, can use for example active component (being transistor).So, adopt term " active matrix ", wherein can divide into two types:

1. as the MOS on the silicon wafer of substrate (MOS) transistor.

2. as the thin film transistor on the sheet glass of substrate (TFT).

With regard to the situation of Class1, use dynamic scattering or guest-main effect usually as electrooptic effect.Use has limited display sizes as substrate material with silicon single crystal, because the modularization assembling of different branch indicating meters also can cause problem in the joint.

With regard to the situation of preferred more promising type 2, use the TN effect usually as electrooptic effect.

Between two kinds of technology, have any different: by the compound semiconductor TFT that constitutes of CdSe for example, or based on the TFT of polysilicon or non-crystalline silicon.For a kind of technology in back, carrying out deep work in the worldwide.

The TFT matrix is put on the inboard of a sheet glass of indicating meter, and another sheet glass has transparent counter electrode in the inboard.With the size compared of pixel electrode, TFT is very little and in fact image do not had detrimental action.This technology can also be promoted the pictorial display that is used for panchromatic function, wherein with the mosaic block of red, green and blue spectral filter so that filter element each and the opposed mode of switchable pixel arrange.

Term MFK indicating meter comprises any matrix display with integrated non-linear element at this, promptly except active matrix, has the indicating meter of passive element in addition, like VR or diode (MIM=metal-insulator-metal type).

This type MFK indicating meter is specially adapted to the high information display that TV uses (for example pocket TV) or is used for automobile or aircraft system.Except dependence of angle and the problem of time of response, because the not high enough ratio resistance of liquid crystal compound yet produces some difficulties [TOGASHI, S., SEKIGUCHI in the MFK indicating meter about contrast gradient; K., TANABE, H., YAMAMOTO, E.; SORIMACHI, K., TAJIMA, E.; WATANABE, H., SHIMIZU, H.; Proc.Euro-display 84, Sept.1984:A210-288 Matrix LCD Controlled by Double Stage Diode Rings, pp.141ff., Paris; STROMER, M., Proc.Eurodisplay 84, Sept.1984:Design of Thin Film Transistors for Matrix Adressing of Television Liquid Crystal Displays, pp.145ff., Paris].Along with the resistance that reduces, the contrast gradient deterioration of MFK indicating meter.Because since with the interaction of indicating meter internal surface; The common life-span with the MFK indicating meter of the ratio resistance of liquid crystal compound descends, and therefore high (initially) resistance is for must being very important for long running has acceptable resistance value in the time indicating meter.

Therefore, existing to having very high ratio resistance and have the very big demand of the MFK indicating meter of big operating temperature range, short response time and low threshold voltage simultaneously, and can produce various GTGs by means of this indicating meter.

The shortcoming of normally used MFK-TN indicating meter is owing to they low relatively contrast gradients, high relatively view angle dependency and in these indicating meters, produce the difficulty of GTG.

The VA indicating meter has significantly preferably view angle dependency and therefore is mainly used in televisor and watch-dog.Yet, still need improve the time of response here, particularly with regard to using televisor with frame frequency (image change frequency/refresh rate) greater than 60Hz.Yet some performances for example low-temperature stability must not be compromised simultaneously.

The present invention is based on such task: liquid crystal compound is provided, and especially for the liquid crystal compound of watch-dog and TV application, it is based on ECB effect or IPS or FFS effect, and it does not have or only on less degree, have above mentioned shortcoming.Particularly; For watch-dog and televisor; Even must guarantee the reliability properties that they also can be worked and have short response time simultaneously and have improvement simultaneously under very high and low-down temperature, particularly do not have or has significantly reduced image retention after the time at long running.

Astoundingly,, particularly in having the liquid crystal compound of negative dielectric anisotropic, use the polar compound of general formula I, then can improve rotary viscosity and therefore improve the time of response if at the liquid crystal compound that is preferred for the VA indicating meter.

So-called monokaryon compound (Einkerner) (compound with a ring) is usually because the phase performance of difference and low clearing point and therefore can not be used for the nematic liquid crystal mixture.Yet the compound of formula I has low-down rotary viscosity and high dielectric anisotropy absolute value astoundingly simultaneously.Therefore can make the liquid crystal compound of the low-temperature performance that has short response time, becomes reconciled with the phase performance of fashion, preferred VA mixture.

Therefore the present invention relates to the liquid crystal media that comprises at least a formula I compound.The invention still further relates to the compound of formula I.

Preferably demonstrate according to mixture of the present invention and to have >=70 ℃, the nematic phase range of the non-constant width of preferred >=75 ℃, clearing point particularly >=80 ℃; Very favorable capacitive character threshold value, high relatively maintenance ratio and while extraordinary low-temperature stability and low-down rotary viscosity and short time of response under-20 ℃ and-30 ℃.Characteristic according to mixture of the present invention also is, except rotary viscosity γ ₁Improvement outside, can observe in order to improve the high relatively elastic constant K of time of response ₃₃Value.

Provide certain preferred embodiments as follows according to mixture of the present invention.

In the compound of formula I, R ¹And R ^1*Preferably represent the straight chain alkoxyl group separately independently of one another, be in particular OC ₂H ₅, OC ₃H ₇, OC ₄H ₉, OC ₅H ₁₁, OC ₆H ₁₃, also have alkene oxygen base in addition, be in particular OCH ₂CH=CH ₂, OCH ₂CH=CHCH ₃, OCH ₂CH=CHC ₂H ₅, also have alkyl in addition, be in particular n-C ₃H ₇, n-C ₄H ₉, n-C ₅H ₁₁, n-C ₆H ₁₃

Particularly preferably, R ¹And R ^1*Expression has straight chain alkoxyl group, particularly oxyethyl group, butoxy, pentyloxy, the hexyloxy of 1-6 C atom or has straight alkenyloxy, the especially OCH of 2-6 C atom independently of one another separately ₂CH=CH ₂

Preferred formula I compound is the compound of formula I-1 to I-10,

Wherein

Alky1 and Alky1 ^*Represent to have the straight chained alkyl of 1-6 C atom separately independently of one another, Alkeny1 and Alkeny1 ^*Represent to have the straight-chain alkenyl of 2-6 C atom separately independently of one another, Alkoxy and Alkoxy ^*Represent to have the straight chain alkoxyl group of 1-6 C atom separately independently of one another, and L ¹And L ²Represent F or Cl separately independently of one another.

In the compound of formula I-1 to I-10, L ¹And L ²Preferably represent F or Cl separately independently of one another, be in particular F.The compound of special preferred formula I-6.In formula I-6, L preferably ¹=L ²=F.

The compound that very especially preferably comprises at least a formula I-6A or I-6B according to mixture of the present invention:

Very particularly preferably comprise at least a compound that is selected from down group according to mixture of the present invention:

In the compound of formula I and minor, L1 and L2 preferably represent F or Cl separately independently of one another, are in particular F.R1 and R1* preferably all represent alkoxyl group.

The compound of formula I can for example be prepared as follows:

Scheme 1

(R and R' respectively do for oneself and have the alkyl of 1-6 C atom)

Scheme 2

(R and R' respectively do for oneself and have the alkyl of 1-6 C atom)

The invention still further relates to the compound of formula I-6A-1 to I-6A-14 and I-8A-1 to I-8A-12.

According to medium of the present invention preferably comprise a kind of, two kinds, three kinds, four kinds or more kinds of, the compound of preferably a kind of, two or three formula I.

Based on whole mixture meter, the compound of formula I is preferably with >=1 weight %, and the amount of preferred >=5 weight % is used for liquid crystal media.The liquid crystal media of compound that especially preferably comprises one or more formulas I of 2-15 weight %.

According to the preferred embodiment of liquid crystal media of the present invention below shown in:

A) comprise the liquid crystal media that one or more are selected from the compound of formula IIA, IIB and IIC compound in addition:

Wherein

R ^2A, R ^2BAnd R ^2CRepresent H separately independently of one another, have at the most that the alkyl and the said alkyl of 15 C atoms do not replace, by CN or CF ₃The single replacement perhaps, replaced by the halogen list at least, wherein one or more CH in these groups ₂All right quilt-the O-of group ,-S-, -C ≡ C-,-CF ₂O-,-OCF ₂-,-OC-O-or-O-CO-so that the O atom not each other directly the mode of keyed jointing replace,

L ^1-4Represent F, Cl, CF separately independently of one another ₃Or CHF ₂,

Z ²And Z ²' represent independently of one another separately singly-bound ,-CH ₂CH ₂-,-CH=CH-,-CF ₂O-,-OCF ₂-,-CH ₂O-,-OCH ₂-,-COO-,-OCO-,-C ₂F ₄-,-CF=CF-,-CH=CHCH ₂O-,

P representes 1 or 2,

Q represent 0 or 1 and

V representes 1-6.

In the compound of formula IIA and IIB, Z ²Can have identical or different implication.In the compound of formula IIB, Z ²And Z ²' can have identical or different implication.

In the compound of formula IIA, IIB and IIC, R ^2A, R ^2BAnd R ^2CPreferred separately expression has the alkyl of 1-6 C atom, is in particular CH ₃, C ₂H ₅, n-C ₃H ₇, n-C ₄H ₉, n-C ₅H ₁₁

In the compound of formula IIA and IIB, L ¹, L ², L ³And L ⁴Preferred expression L ¹=L ²=F and L ³=L ⁴=F, L in addition ¹=F and L ²=Cl, L ¹=Cl and L ²=F, L ³=F and L ⁴=Cl, L ³=Cl and L ⁴=F.Z in formula IIA and IIB ²And Z ²' preferably represent singly-bound separately independently of one another, and also have-C ₂H ₄-bridge.

If Z in formula IIB ²=-C ₂H ₄-, Z then ²' be preferably singly-bound, if perhaps Z ²The C of '=- ₂H ₄-, Z then ²Be preferably singly-bound.In the compound of formula IIA and IIB, (O) C _vH _2v+1Preferred expression OC _vH _2v+1, also have C _VH _2v+1In the compound of formula IIC, (O) C _vH _2v+1Preferred expression C _vH _2v+1In the compound of formula IIC, L ³And L ⁴Preferably represent F separately.

The compound of preferred formula IIA, IIB and IIC provides below:

Wherein Alky1 and Alky1 ^*Represent to have the straight chained alkyl of 1-6 C atom separately independently of one another.

Preferred especially mixture according to the present invention comprises the compound of one or more formulas IIA-2, IIA-8, IIA-14, IIA-29, IIA-35, IIB-2, IIB-11, IIB-16 and IIC-1.

In whole mixture, the ratio of formula IIA and/or IIB compound is preferably at least 20 weight %.

Preferred especially medium according to the present invention comprise preferred amount for 3 weight %, be in particular the compound of at least a formula IIC-1 of 5 weight % and preferred especially 5-25 weight %,

Wherein Alky1 and Alky1 ^*Has above-mentioned implication.

B) additionally comprise the liquid crystal media of one or more formula III compounds,

Wherein

R ³¹And R ³²Separately independently of one another expression have the straight chain of 12 C atoms at the most alkyl, alkoxyalkyl or alkoxyl group and

representes

Z ³The expression singly-bound ,-CH ₂CH ₂-,-CH=CH-,-CF ₂O-,-OCF ₂-,-CH ₂O-,-OCH ₂-,-COO-,-OCO-,-C ₂F ₄-,-C ₄H ₈-,-CF=CF-.

Preferred formula III compound provides below:

Wherein

Aky1 and Alky1 ^*Represent to have the straight chained alkyl of 1-6 C atom separately independently of one another.

The compound that preferably comprises at least a formula III a and/or formula III b according to medium of the present invention.

The ratio of the compound of formula III in whole mixture be at least 5 weight % preferably.

C) additionally comprise preferred total amount >=5 weight, the liquid crystal media of the following formula: compound of weight % especially >=10

and/or

and/or

Further preferably comprise following formula: compound according to mixture of the present invention

D) additionally comprise the liquid crystal media of four nuclear compounds of one or more following formulas,

Wherein

R ^7-10Have independently of one another in the claim 2 for R separately ^2AOne of indicated implication of institute, and

W and x represent 1-6 separately independently of one another.

The mixture that especially preferably comprises the compound of at least a formula V-9.

E) additionally comprise the liquid crystal media of the compound of one or more formulas Y-1 to Y-6,

R wherein ¹⁴-R ¹⁹Represent to have the alkyl or the alkoxyl group of 1-6 C atom separately independently of one another; Z and m represent 1-6 separately independently of one another; X representes 0,1,2 or 3.

The compound that particularly preferably preferably comprises one or more formulas Y-1 to Y-6 according to medium of the present invention with the amount of >=5 weight %.

F) additionally comprise the liquid crystal media of the fluoro terphenyl of one or more formulas T-1 to T-20,

Wherein

R representes to have the straight chained alkyl or the alkoxyl group of 1-7 C atom, and m=0,1,2,3,4,5 or 6 and n represent 0,1,2,3 or 4.

R preferably representes methyl, ethyl, propyl group, butyl, amyl group, hexyl, methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy.

Preferably comprise formula T-1 to T-21 terphenyl according to medium of the present invention with 2-30 weight %, the particularly amount of 5-20 weight %.

The compound of special preferred formula T-1, T-2, T-20 and T-21.In these compounds, R preferably representes alkyl, and alkoxyl group, has 1-5 C atom separately.In the compound of formula T-20, R preferably representes alkyl or alkenyl, is in particular alkyl.In the compound of formula T-21, R preferably representes alkyl.

If Δ n value >=0.1 of mixture then preferably is used for terphenyl according to mixture of the present invention.Preferred mixture comprise 2-20 weight % one or more be selected from the terphenyl compounds of compound T-1 to T-21.

G) additionally comprise the liquid crystal media of the biphenyl of one or more formulas B-1 to B-3,

Wherein

Alky1 and Alky1 ^*Separately independently of one another the expression have 1-6 C atom straight chained alkyl and

Alkeny1 and Alkeny1 ^*Represent to have the straight-chain alkenyl of 2-6 C atom separately independently of one another.

The ratio of the biphenyl of formula B-1 to B-3 in whole mixture be at least 3 weight % preferably, particularly >=5 weight %.

In the compound of formula B-1 to B-3, the compound of formula B-2 is preferred especially.

Preferred especially biphenyl is

Alky1 wherein ^*Alkyl with 1-6 C atom.The compound that especially preferably comprises one or more formulas B-1a and/or B-2c according to medium of the present invention.

H) comprise the liquid crystal media of the compound of at least a formula Z-1 to Z-7,

Wherein R and Alky1 have aforesaid implication.

I) comprise the liquid crystal media of the compound of at least a formula O-1 to O-16,

R wherein ¹And R ²Have for R ^2AIndicated implication.R ¹And R ²Preferably represent straight chained alkyl separately independently of one another.

Preferred medium comprises the compound of one or more formulas O-1, O-3, O-4, O-5, O-9, O-13, O-14, O-15 and/or O-16.

The compound that very especially preferably comprises formula O-9, O-15 and/or O-16 according to mixture of the present invention especially with the amount of 5-30%.

The compound of preferred formula O-15 and O-16 provides below:

Especially preferably comprise the combination of binuclear compound of three nuclear compounds and one or more formulas O-16a to O-16d of formula O-15a and/or formula O-15b according to medium of the present invention.The overall proportion that the compound of formula O-15a and/or formula O-15b and one or more are selected from the combination of compounds of formula O-16a to O-16d binuclear compound is 5-40%, preferred very especially 15-35%.

Preferred very especially mixture inclusion compound O-15a and O-16a:

Based on whole mixture meter, compound O-15a and O-16a are preferably with 15-35%, and the concentration of preferred especially 15-25% and especially preferred 18-22% is contained in the mixture.

Preferred very especially mixture inclusion compound O-15b and O-16a:

Based on whole mixture meter, compound O-15b and O-16a are preferably with 15-35%, and the concentration of preferred especially 15-25% and especially preferred 18-22% is contained in the mixture.

Preferred very especially mixture comprises following three kinds of compounds:

Based on whole mixture meter, compound O-15a, O-15b and O-16a are preferably with 15-35%, and the concentration of preferred especially 15-25% and especially preferred 18-22% is contained in the mixture.

J) liquid crystal media preferably according to the present invention comprises one or more and has tetralyl or the unitary material of naphthyl, suc as formula the compound of N-1 to N-5,

R wherein ^1NAnd R ^2NHave for R independently of one another separately ^2AIndicated implication, preferably represent straight chained alkyl, straight chain alkoxyl group or straight-chain alkenyl and

Z ¹And Z ²Expression-C independently of one another separately ₂H ₄-,-CH=CH-,-(CH ₂) ₄-,-(CH ₂) ₃O-,-O (CH ₂) ₃-,-CH=CHCH ₂CH ₂-,-CH ₂CH ₂CH=CH-,-CH ₂O-,-OCH ₂-,-COO-,-OCO-,-C ₂F ₄-,-CF=CF-,-CF=CH-,-CH=CF-,-CF ₂O-,-OCF ₂-,-CH ₂-or singly-bound.

K) preferred mixture comprises that the fluoro of chroman, formula PH-1 and PH-2 of one or more difluorodiphenyls that are selected from formula BC and chroman compound, formula CR is luxuriant and rich with fragrance, the compound of the fluoro diphenylene-oxide of formula BF,

Wherein

R ^B1, R ^B2, R ^CR1, R ^CR2, R ¹, R ²Has R separately independently of one another ^2AImplication.C is 0,1 or 2.

Preferably comprise the compound of formula BC, CR, PH-1, PH-2 and/or BF according to mixture of the present invention with the amount of 3-20 weight %, the particularly amount of 3-15 weight %.

The compound of preferred especially formula BC and CR is compd B C-1 to BC-7 and CR-1 to CR-5,

Wherein

Particularly preferably be very much the mixture of the compound that comprises a kind of, two or three formula BC-2.

L) preferred mixture comprises the indane compound of one or more formulas In,

Wherein

R ¹¹, R ¹², R ¹³Represent to have straight chained alkyl, alkoxyl group, alkoxyalkyl or the thiazolinyl of 1-6 C atom separately independently of one another,

R ¹²And R ¹³Also represent halogen in addition, preferred F,

expression

I representes 0,1 or 2.

The compound of the formula In-1 to In-16 that the compound of preferred formula In is mentioned below being:

Particularly preferably be the compound of formula In-1, In-2, In-3 and In-4.

The compound of formula In and minor In-1 to In-16 preferably is used for according to mixture of the present invention with the concentration of >=5 weight %, particularly 5-30 weight % and preferred very especially 5-25 weight %.

M) preferred mixture also comprises the compound of one or more formulas L-1 to L-11,

Wherein

R, R ¹And R ²Have independently of one another in the claim 2 for R separately ^2AIndicated implication, and Alky1 representes to have the alkyl of 1-6 C atom.S representes 1 or 2.

Particularly preferably be the compound of formula L-1 and L-4, particularly L-4.

The compound of formula L-1 to L-11 preferably uses with the concentration of 5-50 weight %, particularly 5-40 weight % and preferred very especially 10-40 weight %.

Preferred especially mixture design provides below: (acronym of use is explained in Table A.N and m represent 1-6 here separately independently of one another).

Mixture according to the present invention preferably comprises

The compound of-Shi I, wherein L ¹=L ²=F and R ¹=R ^1*=alkoxyl group,

-CPY-n-Om, particularly CPY-2-O2, CPY-3-O2 and/or CPY-5-O2 are preferably based on whole mixture meter concentration>5%, 10-30% especially,

And/or

-CY-n-Om, preferred CY-3-O2, CY-3-O4, CY-5-O2 and/or CY-5-O4 are preferably based on whole mixture meter concentration>5%, 15-50% especially,

And/or

-CCY-n-Om, preferred CCY-4-O2, CCY-3-O2, CCY-3-O3, CCY-3-O1 and/or CCY-5-O2 are preferably based on whole mixture meter concentration>5%, 10-30% especially,

And/or

-CLY-n-Om, preferred CLY-2-O4, CLY-3-O2 and/or CLY-3-O3 are preferably based on whole mixture meter concentration>5%, 10-30% especially,

And/or

-CK-n-F, preferred CK-3-F, CK-4-F and/or CK-5-F are preferably based on whole mixture meter concentration>5%, 5-25% especially.

Further preferably comprise the design of following mixture according to mixture of the present invention: (n and m represent 1-6 separately independently of one another).

-CPY-n-Om and CY-n-Om, being preferably based on whole mixture meter concentration is 10-80%,

And/or

-CPY-n-Om and CK-n-F, being preferably based on whole mixture meter concentration is 10-70%,

And/or

-CPY-n-Om and CLY-n-Om, being preferably based on whole mixture meter concentration is 10-80%.

The invention further relates to the electro-optical display that has based on the active array addressing of ECB, VA, PS-VA, IPS or FFS effect, be characterised in that, it comprises according to one of claim 1-9 or multinomial liquid crystal media as dielectric medium.

According to liquid crystal media of the present invention preferably have from≤-20 ℃ to>=70 ℃, especially preferably from≤-30 ℃ to>=80 ℃, very especially preferably from≤-40 ℃ to>=90 ℃ nematic phase.

The word here " has nematic phase " and refers on the one hand and under relevant temperature, do not observe smectic phase and crystallization at low temperatures, and on the other hand, when heat by nematic phase, does not still occur clarifying.Detection under the low temperature is carried out under relevant temperature in flow viscometer and was tested at least 100 hours through storage in the testing cassete with layer thickness of using corresponding to electrooptics.If stability in storage is 1000h or higher under-20 ℃ temperature in corresponding testing cassete, then to be considered under this temperature be stable to this medium.-30 ℃ with-40 ℃ temperature under, the corresponding time is respectively 500h and 250h.Under the high temperature, clearing point is measured through ordinary method in kapillary.

Liquid crystal compound preferably has the nematic phase range of 60K at least and at 20 ℃ of maximum 30mm down ²S ^-1Kinetic viscosity v ₂₀

The value of degree of birefringence Δ n is usually between 0.07 and 0.16, preferably between 0.08 and 0.12 in liquid crystal compound.

Liquid crystal compound according to the present invention has-0.5 to-8.0, and particularly-2.5 to-6.0 Δ ε, wherein Δ ε representes dielectric anisotropy.Rotary viscosity γ under 20 ℃ ₁Be preferably≤165mPas, particularly≤140mPas.

Liquid crystal media according to the present invention has low relatively threshold voltage (V ₀) numerical value.They preferably at 1.7V in the scope of 3.0V, preferred≤2.5V and preferred≤2.3V especially very especially.

For the present invention, unless expressly stated otherwise,, term " threshold voltage " relates to capacitive character threshold value (V ₀), also be known as the Freedericksz-threshold value.

In addition, in liquid crystal cell, have high voltage based on liquid crystal media of the present invention and keep comparing numerical value.

Usually, the liquid crystal media with low addressing voltage or threshold voltage demonstrates than has those lower voltages maintenance ratios of higher addressing voltage or threshold voltage, and vice versa.

For the present invention, term " dielectric positive compounds " expression has Δ ε>1.5 those, term " dielectric neutral compound " expression has-those of 1.5≤Δ ε≤1.5, and term " dielectric negativity compound " expression has Δ ε < those of 1.5.Here, the dielectric anisotropy of compound is confirmed in the following manner: the compound dissolution with 10% in the liquid crystal main body and to be less than have under each situation 20 μ m bed thickness with have a vertical plane with have along the electric capacity of the mixture that under 1kHz, measures in the testing cassete of the surface orientation of face.Measuring voltage is generally 0.5V to 1.0V, but it always is lower than the capacitive character threshold value of each liquid crystal compound that is tried.

Among the present invention indicated all temperature values all in ℃.

Mixture according to the present invention is suitable for all VA-TFT to be used, for example VAN, MVA, (S)-PVA, ASV, PSA (VA that polymkeric substance is kept) and PS-VA (VA of polymer stabilizing).They also are suitable for having IPS (face intra) and the FFS (fringing field switching) of negative Δ ε in addition.

Nematic liquid crystal mixtures comprises two kinds of component A and B usually in indicating meter according to the present invention, and itself is made up of one or more simplification compounds.

Component A has significant negative dielectric anisotropic and gives nematic phase with≤-0.5 dielectric anisotropy.Except the compound of one or more formulas I, it preferably comprises the compound of formula IIA, IIB and/or IIC, and the compound that also has formula III.

The ratio of component A is preferably between 45 and 100%, particularly between 60 and 100%.

For component A, preferably select a kind of (or multiple) to have the simplification compound of the value of Δ ε≤-0.8.This value must be negative more, and then the ratio of A in whole mixture is more little.

B component has significantly to row property

With under 20 ℃, be not more than 30mm ²S ^-1, preferably be not more than 25mm ²S ^-1Kinetic viscosity.

The preferred especially simplification compound of B component is to have under 20 ℃ to be not more than 18mm ²S ^-1, preferably be not more than 12mm ²S ^-1The utmost point LV nematic liquid crystal of kinetic viscosity.

B component is monotropy or enantiotrophy nematic, does not have smectic phase, and can under low-down temperature, prevent smectic phase in liquid crystal compound, to occur.For example, if the various materials of height to row property are added in the mixture of liquid crystall, then these materials can compare through the smectic phase inhibition degree that obtains to row property.

Said mixture can also be chosen wantonly and comprise component C, and it is the compound with dielectric anisotropy of Δ ε >=1.5.Based on whole mixture meter, these so-called positive compounds are contained in the mixture of negative dielectric anisotropic with the amount of≤20 weight % usually.

Many suitable materials are that those skilled in the art are known from document.Particularly preferably be the compound of formula III.

In addition, these mesomorphic phases also can comprise greater than 18 kinds of components, preferred 18 to 25 kinds of components.

Except one or more formulas I compound, this preferably comprises compound and the compound of optional III of 4 to 15, particularly 5 to 12 and preferred especially＜10 kinds formula IIA, IIB and/or IIC mutually.

Except the compound of formula I compound and formula IIA, IIB and/or IIC and optional III, also can add other composition, for example with the whole mixture of as many as 45% but preferably until 35%, particularly add until 10% amount.

Said other composition is preferably selected from nematic or to row property material; Known substance particularly; Be selected from zinin, benzylidene aniline, biphenyl, terphenyl, phenylformic acid phenyl ester or phenylformic acid cyclohexyl ester, hexahydrobenzoic acid phenylester or hexahydrobenzoic acid cyclohexyl ester, Santosol 360, cyclohexyl biphenyl, cyclohexyl ring hexane, cyclohexyl naphthalene, 1,4-dicyclohexyl biphenyl or cyclohexyl pyrimidine, phenyl-or cyclohexyl diox, optional halogenated toluylene, benzyl phenyl ether, tolane and substituted cinnamate derivative.

Be suitable for to characterize by formula IV as the most important compound of the composition of this type mesomorphic phase

R ²⁰-L-G-E-R ²¹ IV

Wherein L and E represent to be selected from by 1 separately, dibasic phenyl ring of 4-and cyclohexane ring, 4; The dibasic biphenyl of 4'-, Santosol 360 and cyclohexyl ring hexane system, 2, the dibasic pyrimidine of 5-and 1; 3-diox ring; 2, the dibasic naphthalene of 6-, two-and the carbocyclic ring or the heterocyclic system of the group formed of tetraline, quinazoline and tetrahydro quinazoline

G representes-CH=CH--N (O)=N-

-CH=CQ- -CH=N(O)-

-C≡C- -CH ₂-CH ₂-

-CO-O- -CH ₂-O-

-CO-S- -CH ₂-S-

-CH=N- -COO-Phe-COO-

-CF ₂O- -CF=CF-

-OCF ₂- -OCH ₂-

-(CH ₂) ₄- -(CH ₂) ₃O-

Perhaps C-C singly-bound,

Q representes halogen, preferred chlorine or-CN, and

R ²⁰And R ²¹Expression has alkyl, thiazolinyl, alkoxyl group, alkoxyalkyl or the alkoxy-carbonyl oxy of as many as 18, preferred 8 carbon atoms of as many as separately, and perhaps in these groups also representes CN, NC, NO ₂, NCS, CF ₃, SF ₅, OCF ₃, F, Cl or Br.

In the great majority of these compounds, R ²⁰And R ²¹Differ from one another in these groups one normally alkyl or alkoxyl group.Substituent other version of suggestion is also used always.Many such materials or its mixture are commercially available acquisitions.All these materials can be through known method preparation in the document.

Self-evidently concerning the technician be for example also can comprise wherein H, N, O, Cl and F by the displaced compound of corresponding isotropic substance according to VA of the present invention, IPS or FFS mixture.

Also can be with for example being disclosed in U.S.6, the polymerizable compound in 861,107, so-called reactive mesogen (RM) joins according in the mixture of the present invention in the concentration based on the preferred 0.12-5 weight of mixture %, preferred especially 0.2-2 weight %.These mixtures can randomly also comprise and for example are described in U.S.6, the initiator in 781,665.Initiator, for example the Irganox-1076 of Ciba company preferably joins in the mixture that comprises polymerizable compound with the amount of 0-1%.This type mixture can be used for the VA pattern (PS-VA) or the PSA (VA that polymkeric substance is kept) of so-called polymer stabilizing, and wherein the polymerization process of reactive mesogen should be carried out in liquid crystal compound.Its prerequisite is that liquid crystal compound itself does not comprise any polymerisable component.

In a preferred embodiment of the invention, polymerizable compound is selected from the compound of formula M,

R ^Ma-A ^M1-(Z ^M1-A ^M2) _m1-R ^Mb M

Wherein each group has following implication:

R ^MaAnd R ^MbRepresent P, P-Sp-, H, halogen, SF separately independently of one another ₅, NO ₂, alkyl, alkenyl or alkynyl, wherein radicals R ^MaAnd R ^MbAt least one preferably represent or comprise group P or P-Sp-,

P representes polymerizable groups,

Sp representes spacer groups or singly-bound,

A ^M1And A ^M2Represent preferably to have aromatics, heteroaromatic, the alicyclic or heterocyclic group of 4-25 annular atoms, preferred C atom separately independently of one another, it also can comprise or comprise condensed ring, and it can be randomly single or polysubstituted by L,

L representes P, P-Sp-, OH, CH ₂OH, F, Cl, Br, I ,-CN ,-NO ₂,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R ^x) ₂,-C (=O) Y ¹,-C (=O) R ^x,-N (R ^x) ₂, optional substituted silyl, have the optional substituted aryl of 6-20 C atom; Perhaps have the straight chain of 1-25 C atom or alkyl, alkoxyl group, alkyl-carbonyl, alkoxy carbonyl, alkyl-carbonyl oxygen base or the alkoxy-carbonyl oxy of branching; Wherein one or more H atoms also can be replaced by F, Cl, P or P-Sp-, preferred P, P-Sp-, H, OH, CH ₂OH, halogen, SF ₅, NO ₂, alkyl, alkenyl or alkynyl,

Y ¹The expression halogen,

Z ^M1Expression-O-,-S-,-CO-,-CO-O-,-OCO-,-O-CO-O-,-OCH ₂-,-CH ₂O-,-SCH ₂-,-CH ₂S-,-CF ₂O-,-OCF ₂-,-CF ₂S-,-SCF ₂-,-(CH ₂) _N1-,-CF ₂CH ₂-,-CH ₂CF ₂-,-(CF ₂) _N1-,-CH=CH-,-CF=CF-,-C ≡ C-,-CH=CH-,-COO-,-OCO-CH=CH-, CR ⁰R ⁰⁰Or singly-bound,

R ⁰And R ⁰⁰Represent independently of one another that separately H perhaps has the alkyl of 1-12 C atom,

R ^xExpression P, P-Sp-, H, halogen has straight chain, branching or the cyclic alkyl of 1-25 C atom, wherein one or more non-conterminous CH ₂Group also can by-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-so that O and/or S atom not each other directly the mode of keyed jointing replace; And wherein one or more H atoms also can be replaced by F, Cl, P or P-Sp-; Optional substituted aryl or aryloxy with 6-40 C atom; The optional substituted heteroaryl or the heteroaryloxy that perhaps have 2-40 C atom

M1 represent 0,1,2,3 or 4 and

N1 representes 1,2,3 or 4,

Wherein be selected from radicals R ^Ma, R ^MbWith among the substituting group L that exists at least one, preferred one, two or three, preferred especially one or two expression group P or P-Sp-or comprise at least one group P or P-Sp-.

Preferred especially formula M compound be following these, wherein:

R ^MaAnd R ^MbRepresent independently of one another separately P, P-Sp-, H, F, Cl, Br, I ,-CN ,-NO ₂,-NCO ,-NCS ,-OCN ,-SCN, SF ₅Or have the straight chain of 1-25 C atom or an alkyl of branching, wherein one or more non-conterminous CH ₂Group also can be separately independently of one another by-C (R ⁰)=C (R ⁰⁰)-,-C ≡ C-,-N (R ⁰⁰)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-so that O and/or S atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms also can replace by F, Cl, Br, I, CN, P or P-Sp-, wherein radicals R ^MaAnd R ^MbAt least one preferably represent or comprise group P or P-Sp-,

A ^M1And A ^M2Represent 1 independently of one another separately, 4-phenylene, naphthalene-1,4-two bases, naphthalene-2; 6-two bases, phenanthrene-2,7-two bases, anthracene-2,7-two bases, fluorenes-2; 7-two bases, tonka bean camphor, flavones, wherein one or more CH groups also can be replaced by N in these groups, hexanaphthene-1; 4-two bases, wherein one or more non-conterminous CH ₂Group also can be replaced by O and/or S, and 1,4-cyclohexylidene, dicyclo [1.1.1] pentane-1,3-two bases, dicyclo [2.2.2] octane-1,4-two bases, spiroheptane-2; 6-two bases, piperidines-1,4-two bases, perhydronaphthalene-2,6-two bases, 1,2; 3,4-naphthane-2,6-two bases, indane-2,5-two bases or octahydro-4; 7-endo-methylene group indane-2,5-two bases, wherein all these groups can not replace or be single or polysubstituted by L

L representes P, P-Sp-, OH, CH ₂OH, F, Cl, Br, I ,-CN ,-NO ₂,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R ^x) ₂,-C (=O) Y ¹,-C (=O) R ^x,-N (R ^x) ₂, optional substituted silyl, have the optional substituted aryl of 6-20 C atom; Perhaps have the straight chain of 1-25 C atom or alkyl, alkoxyl group, alkyl-carbonyl, alkoxy carbonyl, alkyl-carbonyl oxygen base or the alkoxy-carbonyl oxy of branching; Wherein one or more H atoms also can be replaced by F, Cl, P or P-Sp-

P representes polymerizable groups,

Y ¹The expression halogen,

R ^xRepresent P, P-Sp-, H, halogen, have straight chain, branching or the cyclic alkyl of 1-25 C atom, wherein one or more non-conterminous CH ₂Group also can by-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-so that O and/or S atom not each other directly the mode of keyed jointing replace; And wherein one or more H atoms also can be replaced by F, Cl, P or P-Sp-; Optional substituted aryl or aryloxy with 6-40 C atom perhaps have the optional substituted heteroaryl or the heteroaryloxy of 2-40 C atom.

Particularly preferably be very much wherein R ^MaAnd R ^MbIn the compound of formula M of one or two expressions P or P-Sp-.

Be used for being selected from for example following formula according to the suitable and preferred RM of liquid crystal media of the present invention and PS-VA indicating meter or PSA indicating meter:

Wherein each group has following implication:

P ¹And P ²Represent polymerizable groups separately independently of one another; Preferably have at preceding text and hereinafter polymerizable groups for one of pointed implication of P; Special preferred acrylate group, methacrylate based group, perfluoroalkyl acrylate ester group, oxetane groups, vinyl oxygen groups or epoxide group

Sp ¹And Sp ²Represent singly-bound or spacer separately independently of one another, preferably have at preceding text and hereinafter isolation group for one of pointed implication of Sp, and especially preferably-(CH ₂) _P1-,-(CH ₂) _P1-O-,-(CH ₂) _P1-CO-O-or-(CH ₂) _P1-O-CO-O-, wherein p1 is the integer of 1-12, and carries out with being connected through the O atom of adjacent ring in the group of wherein mentioning at last, wherein group P ¹-Sp ¹-and P ²-Sp ²-in one also can represent R ^Aa,

R ^AaRepresent H, F, Cl, CN or have the straight chain of 1-25 C atom or the alkyl of branching, wherein one or more non-conterminous CH ₂Group also can be separately independently of one another by C (R ⁰)=C (R ⁰⁰)-,-C ≡ C-,-N (R ⁰)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-so that O and/or S atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms also can be by F, Cl, CN or P ¹-Sp ¹-replace; Special straight chain that preferably has a 1-12 C atom or branching, singly optional or many fluoric alkyl, alkoxyl group, thiazolinyl, alkynyl, alkyl-carbonyl, alkoxy carbonyl or alkyl-carbonyl oxygen base (wherein thiazolinyl and alkynyl have at least two C atoms and the branching group has at least three C atoms)

R ⁰, R ⁰⁰Separately independently of one another and when occurring, represent H at every turn identical or differently or have the alkyl of 1-12 C atom,

R ^yAnd R ^zRepresent H, F, CH separately independently of one another ₃Or CF ₃,

Z ^M1Expression-O-,-CO-,-C (R ^yR ^z)-or-CF ₂CF ₂-,

Z ^M2And Z ^M3Separately independently of one another expression-CO-O-,-O-CO-,-CH ₂O-,-OCH ₂-,-CF ₂O-,-OCF ₂-or-(CH ₂) _n-, wherein n is 2,3 or 4,

L representes F, Cl, CN at every turn identical or differently or has straight chain or branching, optional list or many fluoric alkyl, alkoxyl group, thiazolinyl, alkynyl, alkyl-carbonyl, alkoxy carbonyl or the alkyl-carbonyl oxygen base of 1-12 C atom when occurring; Preferred F

L' and L " represent H, F or Cl separately independently of one another,

R representes 0,1,2,3 or 4,

S representes 0,1,2 or 3,

T represent 0,1 or 2 and

X representes 0 or 1.

Suitable polymerizable compound is for example listed among the table D.

Liquid crystal media based on the application preferably comprises total 0.1-10%, preferred 0.2-4.0%, the polymerizable compound of preferred especially 0.2-2.0%.

The polymerizable compound of special preferred formula M.

Can comprise conventional additives or auxiliary agent in addition according to mixture of the present invention, for example stablizer, inhibitor, UV absorption agent, nano particle, micron particle etc.

According to the structure of liquid-crystal display of the present invention corresponding to common geometry, as for example being described among the EP-OS0240379.

Following examples be used for explaining invention and unrestricted it.Preceding text and hereinafter, per-cent data representation weight percent; All temperature are with a degree centigrade expression.

Run through the application, 1,4-cyclohexylidene ring and 1,4-phenylene ring is represented as follows:

Except the compound of the compound of formula IIA and/or IIB and/or IIC, one or more formulas I, preferably comprise the compound that one or more are selected from below table A according to mixture of the present invention.

Table A

Abbreviation below using:

(n, m, m', z: be 1,2,3,4,5 or 6 separately independently of one another; (O) C _mH _2m+1Expression OC _mH _2m+1Or C _mH _2m+1)

Liquid crystal compound that can be used according to the invention prepares with the mode of routine itself.Usually, the component of using with lesser amt of desired amount is dissolved in the component that constitutes chief component, advantageously carries out at elevated temperatures.Also can blending ingredients in organic solvent, the solution in acetone, chloroform or methyl alcohol for example, and after thoroughly mixing, for example remove again and desolvate through distillation.

By means of suitable additive, modification is according to mesomorphic phase of the present invention by this way: make them can be used for disclosed up to now any kind for example in ECB, VAN, IPS, GH or the ASM-VA LCD display.

Said dielectric medium can also comprise well known by persons skilled in the art and be described in the other additive in the document, for example UV absorption agent, inhibitor, nano particle and free-radical scavengers.Heterogeneous colours, stablizer or the chiral dopant that for example can add 0-15%.Be used for being in particular those of listing in table B according to the suitable stabilizers of mixture of the present invention.

For example; The heterogeneous colours that can add 0-15%; Can also add conducting salt, the complex salts of the preferred own oxybenzoic acid salt of ethyl dimethyl-dodecyl ammonium-4-, TBuA tetraphenyl borohydride salts or crown ether (referring to for example Haller etc., Mol.Cryst.Liq.Cryst. the 24th volume; 249-258 page or leaf (1973)), perhaps can add some materials to change dielectric anisotropy, viscosity and/or nematic orientation to improve conductivity.This type substance description is in DE-OS2209127,2240864,2321632,2338281,2450088,2637430 and 2853728 for example.

Shown among the table B and can add according to the possible doping agent in the mixture of the present invention.If this mixture comprises doping agent, then it uses with the amount of 0.01-4 weight %, preferred 0.1-1.0 weight %.

Table B

Illustrated among the following table C can be for example based on the amount of the mixture meter at the most the amount of 10 weight %, preferred 0.01 to 6 weight %, particularly 0.1 to 3 weight % add according to the stablizer in the mixture of the present invention.Preferred stablizer is in particular the BHT verivate, and for example 2,6-di-t-butyl-4-alkylphenol and Tinuvin 770.

Table C

(n=1-12)

N=1,2,3,4,5,6 or 7

N=1,2,3,4,5,6 or 7

Illustrated among the following table D and preferably in PSA and PS-VA application, be used for suitable reactive mesogen according to mixture of the present invention:

Table D

Embodiment:

Following embodiment should be used for explaining the present invention rather than limiting it.In an embodiment, F. represent fusing point and K represent in degree centigrade the clearing point of liquid crystal material; Boiling point is represented by Kp..In addition:

K representes crystalline solid state, and S representes smectic phase (exponential representation facies type), and N representes nematic state, and Ch representes cholesteryl phase, and I representes isotropic phase, T _gThe expression second-order transition temperature.The transition temperature of the numeral degree centigrade meter between two symbols.

As the main body mixture of the optical anisotropy Δ n that is used to measure formula I compound is the mixture ZLI-4792 (Merck KGaA company) that commerce is buied.Use the commercial mixture ZLI-2857 that buys for measuring dielectric anisotropy Δ ε.The physical data of compound to be studied adding compound to be studied be extrapolated to 100% compound that uses after by the variation acquisition of the specific inductivity of main body mixture.Depend on solvability, generally speaking 10% compound to be studied is dissolved in the main body mixture.

Unless otherwise indicated, part or per-cent data representation weight part or weight percent.

Conventional processing is represented: adds entry, uses dichloromethane extraction, separate, and dry organic phase, evaporation, and through crystallization and/or chromatogram purified product.

Embodiment 1

With 100g (0.54mol) 2,3-difluoro butyl phenyl ether is introduced among the 750ml THF and is cooled to-70 ℃ at first.Drip the 1.6M solution (0.57mol) of 360ml n-Butyl Lithium in hexane then.Stirred one hour down at-70 ℃ again, and drip 66ml (0.59mol) trimethyl borate in 100ml THF subsequently.Batch of material is heated to 0 ℃, and adds 46ml Glacial acetic acid min. 99.5 and 100ml water.Drip 140ml hydrogen peroxide (30%) down at 30 ℃ then.During this period, reaction mixture becomes warm to about 45 ℃.Before carrying out conventional processing, make mixture be cooled to room temperature and restir 1h.This obtains the 78g crude product, under having the situation of further purifying, it is not dissolved in the 200ml second ketone, and adds 0.4mol normal-butyl bromination thing and 0.5mol salt of wormwood.Under refluxing, boil and spend the night and carry out conventional processing.Carry out last purifying through distilling down with 107-110 ℃ of boiling temps at 0.5 millibar.

K-8I；Δn=0.0832；Δε=-8.6

The compound for preparing following formula similarly:

Embodiment 2

With 10g 4-propoxy--2,3-difluorophenol (53mmol) boils under refluxing with 8.4g 3-bromo-1-propylene (69mmol) and 8.1g salt of wormwood and spends the night.Carry out conventional processing, and 0.5 millibar with 88-90 ℃ of boiling temperature under distillation residue.

T _g-86K-38I；Δn=0.0873；Δε=-7.7

The compound for preparing following formula similarly:

At preceding text and hereinafter,

V ₀The expression threshold voltage, under 20 ℃ capacitive [V],

Δ n is illustrated in 20 ℃ of optical anisotropies of measuring down with 589nm,

Δ ε be illustrated in 20 ℃ with 1kHz under dielectric anisotropy,

Cp. represent clearing point [℃],

K ₁The expression elastic constant, " tiltedly exhibition " distortion [pN] under 20 ℃,

K ₃The expression elastic constant, " bending " distortion [pN] under 20 ℃,

γ ₁Be illustrated in the rotary viscosity [mPas] that records under 20 ℃, it is through rotational method

In magnetic field, record

LTS representes low-temperature stability (nematic phase), and it is measured in testing cassete

The indicating meter that is used for measurement threshold voltage has two parallel plane carrier boards and the electrode layer at interval with 20 μ m; And electrode layer has the oriented layer of SE-1211 placed on it (Nissan Chemicals) on the medial surface of carrier board, and it plays the effect that makes liquid crystal vertical plane orientation.

What all concentration related in this application is corresponding mixture or component of mixture, unless expressly stated otherwise.All physical propertiess are according to " Merck Liquid Crystals; Physical Properties of Liquid Crystals ", Status November 1997, Merck KGaA; (Germany) measures and is applicable to 20 ℃ temperature, unless expressly stated otherwise.

Mixture embodiment

Embodiment M1

Embodiment M2

Embodiment M3

Embodiment M4

Embodiment M5

Embodiment M6

Embodiment M7

Embodiment M8

Embodiment M9

Embodiment M10

Embodiment M11

Embodiment M12

Embodiment M13

Embodiment M14

Embodiment M15

Embodiment M16

Embodiment M17

Embodiment M18

Embodiment M19

Embodiment M20

Embodiment M21

Embodiment M22

Embodiment M23

Embodiment M24

Embodiment M25

Embodiment M26

Embodiment M27

Embodiment M28

Embodiment M29

Embodiment M30

Embodiment M31

For preparation PS-VA mixture, with the polymerizable compound of 0.2% following formula

Adding 99.8% derives from the mixture of embodiment M31.

The PS-VA mixture is filled in the box with vertical plane orientation.After applying 24V voltage, use power 100mW/cm ²The UV rayed.Following pitch angle appears then:

Embodiment M32

Embodiment M33

Embodiment M34

Embodiment M35

Embodiment M36

Embodiment M37

Embodiment M38

For preparation PS-VA mixture, with the polymerizable compound of 0.3% following formula

Adding 99.7% derives from the mixture of embodiment M37.

The PS-VA mixture is filled in the box with vertical plane orientation.After applying 24V voltage, use power 100mW/cm ²The UV rayed.

Embodiment M39

Adding 99.7% derives from the mixture of embodiment M37.

The PS-VA mixture is filled in the box with vertical plane orientation.After applying 24V voltage.

Use power 100mW/cm ²The UV rayed.

Embodiment M40

Adding 99.7% derives from the mixture of embodiment M37.

The PS-VA mixture is packed in the box with vertical plane orientation.After applying 24V voltage, use power 100mW/cm ²The UV rayed.

Claims

1. based on the liquid crystal media of the mixture of polar compound, be characterised in that it comprises the compound of at least a formula I,

Wherein

R ¹And R ^1*Represent to have the alkyl or the alkoxyl group of 1-15 C atom separately independently of one another, wherein one or more CH in these groups ₂Group also can be separately independently of one another by-C ≡ C-,-CF ₂O-,-CH=CH-,

-O-,-CO-O-,-O-CO-so that the O atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms also can by halogen replace and

2. according to the liquid crystal media of claim 1, be characterised in that it comprises the compound that one or more are selected from formula IIA, IIB and IIC compound in addition:

Wherein

R ^2A, R ^2BAnd R ^2CRepresent H separately independently of one another, have at the most that the alkyl and the said alkyl of 15 C atoms do not replace, by CN or CF ₃The single replacement perhaps, at least singly replaced by halogen, wherein one or more CH in these groups ₂Group also can by-O-,-S-,

-C ≡ C-,-CF ₂O-,-OCF ₂-,-OC-O-or-O-CO-so that the O atom not each other directly the mode of keyed jointing replace,

L ^1-4Represent F or Cl separately independently of one another,

P representes 1 or 2,

Q represent 0 or 1 and

V representes 1-6.

3. according to the liquid crystal media of claim 1 or 2, be characterised in that it comprises the compound of one or more formula IIIs in addition,

Wherein

means

Z ³The expression singly-bound ,-CH ₂CH ₂-,-CH=CH-,-CF ₂O-,-OCF ₂-,-CH ₂O-,-OCH ₂-,-COO-,-OCO-,-C ₂F ₄-,-C ₄H ₉-,-CF=CF-.

4. according to one or the multinomial liquid crystal media of claim 1-3, be characterised in that said medium comprises the compound of at least a formula I-1 to I-10:

Wherein

Alkyl and Alkyl ^*Represent to have the straight chained alkyl of 1-6 C atom separately independently of one another,

Alkenyl and Alkenyl ^*Represent to have the straight-chain alkenyl of 2-6 C atom separately independently of one another,

Alkoxy and Alkoxy ^*Represent to have the straight chain alkoxyl group of 1-6 C atom separately independently of one another,

L ¹And L ²Represent F or Cl separately independently of one another.

5. according to one or the multinomial liquid crystal media of claim 1-4, be characterised in that said medium comprises the compound of at least a formula L-1 to L-11 in addition:

Wherein

R, R ¹And R ²Have independently of one another in the claim 2 for R separately ^2AIndicated implication, and Alkyl represent to have 1-6 C atom alkyl and

S representes 1 or 2.

6. according to one or the multinomial liquid crystal media of claim 1-5, be characterised in that said medium comprises the terphenyl of one or more formulas T-1 to T-21 in addition,

Wherein

R represent to have 1-7 C atom straight chained alkyl or alkoxyl group and

M representes 1-6.

7. according to one or the multinomial liquid crystal media of claim 1-6, be characterised in that said medium comprises the compound of one or more formulas O-1 to O-16 in addition,

Wherein

R ¹And R ²Have independently of one another in the claim 2 for R separately ^2AIndicated implication.

8. according to one or the multinomial liquid crystal media of claim 1-7, be characterised in that said medium comprises the indane compound of one or more formulas In in addition,

Wherein

R ¹¹, R ¹², R ¹³Expression has straight chained alkyl, alkoxyl group, alkoxyalkyl or the thiazolinyl of 1-5 C atom,

R ¹²And R ¹³Also represent halogen in addition,

expression

I representes 0,1 or 2.

9. according to one or the multinomial liquid crystal media of claim 1-8, be characterised in that in whole mixture that the ratio of formula I compound is >=1 weight %.

10. preparation is characterised in that at least a formula I compound is mixed with at least a other liquid crystalline cpd, and randomly adds additive according to the method for of claim 1-9 or multinomial liquid crystal media.

11. be used for the application of electro-optical display according to one of claim 1-9 or multinomial liquid crystal media.

12. have the electro-optical display of active array addressing, be characterised in that it comprises according to one of claim 1-9 or multinomial liquid crystal media as dielectric medium.

13., be characterised in that it is VA, PSA, PS-VA, PALC, FFS or IPS indicating meter according to the electro-optical display of claim 12.

14. the compound of following formula